Epoxide, diphenolic acid aldehyde condensates



use Ja s United States PatentOfifice S ylvan'Dwen Greenle e, west Lafayette-1nd assignor t S. C. Johnson & Son, Inc., Racine, Wis.

, i No Drawing. Application August 8, 1958 'Serial No. 753,867

Claims. (Cl. 260- 19) 1 This inventionrelates to new eompositions resulting from the reaction of epoxides and aldehyde condensates to give valuable eompositions for use in the manufacture of coating compositions, molding compositions, adhesives, etc. The aldehyde condensates contain reactive hydrogen containing groups including hydroxyl and ,carboxyl groups. 'I'hesefgroups react with the epoxide compositions which contain anaverage of more than one epoxide group per molecule. The compositions include the initial reaction mixtures as Well as intermediate and final reaction products derived therefrom.

An object of this invention is to provide new admixtures containing polyepoxides and aldehyde condensates having carboxyl groups and other active hydrogen containing groups so that they may undergo reaction to form polymer products of varying complexity.

Another object of this invention is to provide from the reaction of polyepoxides and aldehyde condensates having carboxyl and other active hydrogen containing groups new compositions which are valuable in the manufacture of protective coatings, films, molded articles, adhesives, etc. i r The foregoing and other objects and advantages are attained by the present invention, various novel features of which will become more fully apparent from the description, with particular reference to specific examples which are to be considered as illustrative only.

In general, the compositions of this invention are prepared by reactingcondensates of phenolic acids and aldehydes, particularly formaldehyde, having reactive hydrogen containing groupsincluding carboxyl groups, with polyepoxide compositions containing an average of more than one epo xide group. per molecule and are free from functional groups other than epoxide or hydroxyl. The

activehydrogen containing condensates react with the epoxide groups of the polyepoxide compositions to form polymer products of varying complexity.

- OPERABLE ALDEHYDE CONDENSATES The aldehyde condensates employed in this invention are prepared by the condensation of aldehydes with pheradical of, at least 2 carbon atoms; however, experience in thepreparation of ,bisphenol'l and related compounds indicates ,that the carbonyl group of theketo acid should be positioned next to awterminal methyl group. in order to,obtain satisfactoryyield s. Further, while a broad class of acids is contemplated "such as the keto substituted pentanoic, hexanoic and hepta'noic acids, the pentanoic acid, levulinic acid, is preferred since it is readily available.

Prior applications, Serial Nos. 464,607 and 489,300 filed October 25, 1954, and February 18, 1955, respectively, disclose a number of illustrative compounds suitable for use as the diphenolic acid and methods of preparing the same. These materials which. are referred to for convenience as biphenolic acids Diphenolic Acid or by the trade name DPA, consist of the condensation products of Ievulinic acid and phenol, substituted phenols or mixtures thereof. It is to be understood that the phenolic nuclei of the diphenolic acid may be substituted with any group which will not interfere with the reactions contemplated herein. Such groups are the halo, nitro and alkyl groups of 1 to 5 carbon atoms. The chloro and bromo phenols are the preferred halogenated materials although it is possible to condense fluoro substituted phenols with a keto acid. Biphenolic acids derived from substituted phenols such as the alkylated phenols are sometimes more desirable than the products obtained from unsubstituted phenols due to properties imparted by the substituted groups. For instance,the alkyl groups provide better organic solvent solubility, flexibility and water resistance. However, the unsubstituted product is usually more readily purified. In the before mentioned condensation reaction. between the phenol and keto acid it has been found, as one would expect, that the reaction occurs so that the phenolic hydroxyl group of the. bi-.

phenolic acid is in a position para or ortho to the point.

of attachment of the hydroxyaryl radical to the pentanoic acid. Very little or no condensation occurs at. the-meta.

position.

Suitable aldehydes operable in the subject condensates are the low molecular weight mono aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, furfural, etc.1

However, because of commercial availability as well as its greater reactivity, formaldehyde is preferred. It is to be understood, however, that any aldehyde reactive with a phenolic compound is operable for purposes of 1 this invention.

The diphenolic acid reacts with the aldehydes, for ex-i ample, formaldehyde, to yield initially an alkylol condensation product which can be illustrated by the fol-. lowing formula representing the alkylol condensation In the condensation reaction with aldehydes, the phe- 1 nolic hydroxyl groups serve to activate the aromatic densation to take place, the substitution should not be so complete as to remove 'all hydrogen atoms from these ortho and para positions. These alkylol condensatesare converted to polymers by the application of heat, I molecules or Diphenolic Acid combining with each otl ler nuclei at the ortho and para positions with respect ;to the hydroxyl groups. Addition, therefor, occurs pri-' The Diphenolic Acid, 4,4-bis" (4-hydroxyphenyl)pentanoic acid, has two such hydro gen-containing carbon atoms in each of the aromatic". nuclei of the acid, so that up to 4 mols of aldehyde may marily at these positions.

be reacted readily with each mol of'acid. In those cases where alkyl groups or halides have been substituted in the aromatic nuclei of the acid, for appreciable con- Patented Oct. 6, i959 through methylene bridges to form polycarboxylic acids. In those cases where alkylol form is preparedwith the addition of aldehyde to substantially all the free ortho and parapositions in the acid, polymerization occurs with the splitting ofi of alkylol groups and the liberation of aldehyde. A typical polymerization reaction might be illustrated as follows:

OH ([)H GHsOH heat o on, 0111011300211 011 OH" OH OH I out on,

O C Q; CHgCHgCOgH oh, OH CHzOOgH Slightly modified products may be obtained by using the Diphenolic Acid in combination with other materials capable of condensing with an aldehyde. Such materials may be illustrated by the mononuclear, polynuclear, monohydric or polyhydric phenols or ammonia derivatives containing at least one NH group, with at least one ofthe free valency bonds .of the nitrogen atom being attachedto a carbon atom and the remaining valency bond to carbon or hydrogen. Exemplary phenols are hydroxybenzene, the cresols, xylenols, butylphenol, naphthols, andv bis(4-hydroxyphenyl) isopropylidene. Operable ammonia derivatives can be illustrated by primary and secondary amines, amides, or derivatives thereof. These materials, referred to herein as modifiers, may be first partially condensed with aldehydes and then-admixed with a partially condensed mixture of diphenolic .acid and aldehyde to yield, after further condensation, valuable complex products. The further condensation referred to can occur by simply admixing the condensates and heating or by admixing the condensates with a polyepoxide, applying the-admixture to a suitable substrate such as glass or tin and heating, the conversion reaction taking place directly on the substrate. Alternatively, these. materials may be admixed prior to condensation with a Diphenolic Acid and aldehyde to yield, after condensation a similarly modified product. In such instances, the condensates contain, in addition to alkylol hydroxyl groups, phenolic hydroxyl groups, groups containing an active hydrogen attached to a nitrogen atom, and carboxylic acid groups. In the more highly condensed condensates where most of the methanol groups have been dehydrated to form methylene linkages, the compositions contain primarily phenolic hydroxyl and carboxylic acid groups.

The. .aldehyde condensates described liereinabove are ingeneral, partial and intermediate reaction or condensation products of aldehydes and biphenolic acids or condensation products of aldehydes, biphenolic acids and modifying materials. It is important that the condensation is=not carried so far as to produce aninfusible and insoluble material.- In. general the condensate can be in,its mon'omerictorm, which is essentially an alkylol or polyalkylol product or. it can be quite highly condensed.

I It iSJSuitabIe as long as it is still fusible and soluble in or 1 compatible with the epoxide composition.

Reactions of the Diphenolic ,Acid with. an aldehyde,

and if desired a rnodifier, can be ,conveniently carried out.,.by.processes known in the art.

q t For example, the react on between a Diphenolic Acid, and formaldehyde Will proceed readily at from 40 to 60 C. without a, catalyst.

However, since the reaction is quite slow, as a more practicable application either an acid or an alkaline catalyst is used to accelerate the reaction. By choosing a specific catalyst, one can obtain some control of the type of product formed. The most effective acid catalysts are oxalic, sulfuric, para-toluenesulfonic, and hydrochloric acids, but in some instances acid salts are also operable. Further, a variety of basic materials may serve ascatalysts. These include sodium hydroxide, zinc oxide, ammonia, 'morpholine, and other amines. 'When the'reaction is finished the reaction mixture can be neutralized, if an excess of acid or alkali were used, and subsequently washed with water. However, in many instances, it is not necessary to neutralize the reaction mixture and a simple decantation of the aqueous layer is suflicient.

The decision to choose an acid or basic type catalyst is based primarily on the use for which the resin is intended and the amount of formaldehyde that is to be combined with the phenolic material. In general it can system used as well as the catalyst employed. If relatively low rather than higher temperatures are employed, the reaction takes a relatively longer time to go to completion. Although the temperature of the reaction is relatively non-critical, the reactions are preferably carried out at temperatures ranging from 40 to 110? -C. or at reflux temperatures. Further, the condensation can be carried out with or without the presence of organic solvents and alone or in combination with other reactants.

In certain cases where the Diphenolic Acid and modify ing material used in the reaction are fairly insoluble in water it may be desirable to use organic solvents to carry out the reaction. In addition, in those instances where the condensate is used together with other materials in the production of complex products, it is possible to carry out the condensation reaction simultaneously with other reactions, for example, a mixture of Diphenolic Acid, aldehyde and a polyepoxide resin will form a suitable composition for certain applications.

Proportions of aldehyde to phenolic acid'can vary from about 0.5 mol of the aldehyde per mol of acid up to about 4 mols of the aldehyde to 1 mol of the acid. It

is to be understood that as the ratio of the aldehyde is increased, the complexity of the resultant polymer is also increased. Further, part of the phenolic acid can be replaced by materials reactive-with an aldehyde, as'hereinbefore described. Usually it is not desirable to replace" densates used in this invention. "However, it should be.

understood that the invention'is not intended to be limited thereby. Proportions expressed are parts by Weight unless otherwise indicated. Acid values 'as used herein represent the number of milligrams of KOH required to neutralize L typical'ammonia' derivative-aldehydecondensates.- The a 1 gram sample. r

' Examples l'to 8 inclusive, illustrate 'the preparation-of phenolic acid-aldehyde condensates. 'Example'9- describes the preparation of a condensation product from a rnix ,ture of a phenol, Diphenolic Acid and an aldehyde;

Examples "10 to 12' inclusive describe thepreparationof phenol-aldehyde condensates using 'butylphenol, 4,4- bis(4-'hydroxyphenyl) isopropylidene and phenol. 'EXT amples 13 to 1,7. inclusive, describe the preparation of condensation of. Examples 10-17 inclusive. a{re .usefuliri conjunction iw ith the condensates of Diphenolic Acid the manufacture of complex reaction products as hereinbefore described.

temperatureof 95 C. The resulting product, amounting to 145 parts, had an acid value of 165. The product was dissolved in'methyl ethyl ketone to give a non-volatile content of 50%. I

Example 2 s Example 3 A mixture of 286 pentanoic acid, 172parts offormalin, and 1.5 parts of sodium hydroxide was refluxed for a period of 1 hour. The product was-freed from water by distillation at a temperature of 100 C. (pot temperature) using a water aspirator vacuum. The product, having an acid value of 169, amounted to 318 parts. This product was dissolved to a non-volatile content of- 50% in methyl ethyl ketone.

Example 4 A mixture of 286 parts of 4,4-bis(4-hydroxyphenyl) pentanoic acid, 258 parts of formalin, and 1.5 parts of sodium hydroxide was refluxed for a period of 1 hour. The productwas freedrfrom water by vacuum distillation .using a water aspirator, heating the mixture to a temperature of 97 C. The product, having an acid value of 151 and amounting to 361 parts, was dissolved in methyl ethyl ketone to give a 50% non-volatile content.

Example 5 A mixture of 286 parts of 4,4-bis(4-hydroxyphenyl)- pentanoic acid, 258 parts of formalin, and .7 part of oxalic acid was refluxed for a period of 1 hour. The water layer was removed by decantation and the organic resin layer washed three times with hot water. The organic resinlayer was finally freed from the last traces of water by vacuum distillation using a water aspirator heating the reaction mixture to a temperature of 94 C. The resulting product, amounting to 343 parts and having an acid value of 131, was dissolved in methyl ethyl ketone to give a non-volatile content of 50%.

Example 6 p A mixture of 94 parts of Diphenolic Acid prepared from ortho cresol and levulinic acid in the manner described in my copending application, Serial No. 489,300, 48parts 37% formaldehyde and 0.5 part sodium hydrox ide fwas charged to a S-necked flask equipped with a thermometer, mechanical agitator, and reflux condenser. The charge was heated to reflux and held for 1 hour. The reaction mixture was allowed to cool and the water layerdecante d. The final trace of water. was stripped parts i of 4,4-bis(4-hydroxyphenyl) Example?"- 1 1 Dichloro DPA wasprepared by charging 363 parts of the ethyl ester of 4,4-bis(4-hydroxyphenyl) pentanoic acid and 344 parts of sulfonyl chloride to a 3-necked flask equipped with thermometer, reflux condenser, and mechanical stirrer. and was cooled with a water bath maintaining the temperature at approximately C. for 1 hour. The reaction charge became thick and then solidified with a pronounced temperature rise. The reaction mixture had a yellow color. Excess sulfonyl chloride was removed under slight pressure. The obtained ester had a chlorine content of 21.38% corresponding to the addition of approximately 2 chlorine atoms (theoretical equals 18.5%). The chlorinated ester was saponified to obtain the corresponding acid. I

parts of dichloro DPA, 32 parts of 37% formaldehyde and 0.4 part sodium hydroxide were charged to a 3- necked flask equipped with thermometer, reflux temperature and held for approximately 3 hours. The reaction mixture was allowed to cool and 100 parts of cold water were added before neutralizing with dilute hydrochloric acid. A gummy resinous precipitate formed. The water layer was decanted and the resin washed 3 times with 60 C. water. The resin was dissolved in 150 ml. of dioxane and filtered to remove insoluble inorganic salts and subsequently stripped under slight pressure to remove final traces of solvent. The product was a resinous solid having an acid value of 128 and a softening point of off undervacuum. ,The resultant product was a viscous resinous material having an acid value of 129 and 1a a e ire aw efio t it s Example 8 Dinitro DPA was prepared by charging 172 parts DPA and 450 parts glacial acetic acid to a B-necked flask equipped with a thermometer, reflux condenser, and mechanical stirrer. Theresultant solution was tan in color. 264 parts of benzene were added to the charge before cooling to 0C. in an ice bath. At this tempera-' of theoretical, had an acid value of 488 (th.eoretical= 447).

and a melting point l024 C. The crude material was recrystallized from a mixture of hot ethanol and water to give a fine yellow crystalline material having a melting point of 137.5-140 C., a nitrogen content of 7.20% (theoretical equals 7.44%) and an acid value of 445.

19 parts of dinitro DPA and 8 parts of 37 formaldehyde and 25 parts concentrated hydrochloric acid were dissolved in ml. of dioxane. charged to a 3-necked flask equipped with thermometer, reflux condenser, and mechanical agitator. The charge was heated to reflux and held for approximately 5 hours. The reaction mixture was allowed to cool and the aqueous layer removed by decantation. The dioxane solution was transferred to a distillation setup and the dioxane stripped off under slight vacuum. The resultant product was.

a resinous solid having an acid value of 367 and a softening point of 29-39 C.

Example 9 oxalic acid was refluxed fora period of lhour and 20 minutes. The water layerwas removed byd'ecantation and the organic resin layer washed two times withihqt The reaction immediately exothermed The mixture was i water. The organic resin layemwa's then freed from the l st race pfiwater y heatingwi havacuum 115mg; a

water] asnir or,iheatingthesmixtu t a emper t re f,

98}? CI The resulting product, having, an acid value of 79, ,was, dissolved, in methyl? ethyl ketone' to a. nonvolatile content of 50 l i Example Amixtureof' 1000 parts of p-tert-butylphenol, 1067' parts of formalii'rand 10p-arts of sodium hydroxide was refluxedfor; a periodofgl" hour at 95? C, The water layer was 'rernovedbydecantation and "the resulting organic layer washed twice withhot water. phenol-formaldehyde resin layer was,dehydrated by re- .dueing 'the pressure with a water aspirator and heating the mixture at50 C. The resulting dehydrated syrupy product amounted to 1470 parts.

I Example :11

'By asimilar process to'that described ingEXample 10, a mixture of 912" parts of' 4,4 bis(4-hydroxyphenyl),-

isopropylidene' was treatedwith' 960parts of formalin 311(122'8 parts'of-oxalic ,acid to give 1065' parts of, a syrupy product; V

. Example 12" By the same procedure as-th'at used'in Exarnple 10,

a mixture-@ 65 S parts-ofiphenol, 1400 parts of -formalin,

and6;6"parts;of sodium-hydroxide gave 1168-parts-of'a syrupy product:

Example 13 In a 3-liter 3-neck flaskprovided With a mechanical agitator, aithermometer, and refluxcondenser was placed 120 -parts of, urea, 600 parts 5 of 37% I aqueous formaldehyde, and 1040. parts of n-butyl alcohol. With continuous agitation the reaction; mixture; -wa s ,heatedto reflux temperature and the refluxingcontinuedfon a period of l hour, At this; point a water trap was, placed-between the;

reflux condenser andflask and filled with toluene. Distil: lation was continued until 315 parts; of;water;'we1:e removed fronr the; reaction ,=mixture. The resultin mixture was cooled .to roomtemperature, filtered, and 1030 parts of a=clear, water-white, syrupy liquid isolated.

Example '14 The, procedure of preparation including the water remoyal=was-the sameas that used in Example 13.

light amber, syrupy product.-

Example 15 The procedure; of preparation including the removal of wateriwastheqsameas that .used in Example 13. A mixture,-,of:120. parts. of urea, 148 parts of thiourea, 950 parts '0fa137% aqueousformaldehyde, and800 parts of n butyl alcohol :,was usedto give a final yield of'1175 parts ,.oi":-a. clear, almost colorless, syrupy liquid.

' Example 16;;

The V mixture. of. 304 p arts of thiourea, 960. parts of'37% aqueous formaldehydaand 800 parts of n-butyl alcohol was used .to give-a final yield of, 1214 P ts of a clear, I

Example 17" In a 3-liter 3-neck flask provided with a mechanical agitator, a thermometer, and arefluX condenser was placed "1370 parts.ofi1prtoluenesulfonamide.andi640 parts of- 37% aqueous formaldehyde ythe-pH-fof whicli'shad been? previously adjusted 1102610 with zpotassiumacid'qphthalate andrisodiuma hydroxide; Withcontinuous agitation: the. reactiorrzmi-xturezwas-.heatedito reflux-.temperature over ia-r period 3 of; 40. i minutes and; the refluxing; continued for: to period of ;15:im-inu tes.a. At :this ipoint-the. reaction mixture was allowedlo cool andzthe water. decanted-ifrom' tlre: resin; The resin was. washed '23 times i withwwarm water;

and finally dehydrated ,in :vacuunt at 2 3 07-'-50 immi pressure;

using a maximum flask temperature at 90.3"C. 'toayieldfi 1245 parts of water white resinimsssolid.

In Examples 1 through 9', inclusive, the Diphenolic Acid can be replaced'by other biph'enolic acids including acids containingchloro; bromo, nitro and alky-l-groupsof 1'to5 carbon atomssuch as 4,4-bis(4-hydroxy-3-ethyl phenyl) pentanoic' acid; 4,4 bis(4-'h ydroxy- 2'- ethyl" phenyl)*--pentanoic aeid,- 4-,'4-'bis(2-- hydrbxy 4- butyl-'- phenyl) pentanoic acid, 4,4-"- bis(4'- hydroxy 3- nitro phenyl) 1- pentanoie'acid; 4;4 -bis(2*- hydroxy- 3 nit'rophenyl) pentanoic acid; 4,4 -bis(4 hydroxymethyl phenylypentanoic acid, 4,4?- bis(4- --h'ydroxy= 3 amyl phenyl) pentanoic acid, 4-,'4"- bis(4"- hydroxy- 3 chloro phenyl) pentanoicacid, 4 (4 hydroxyphenyl) 4 (4 hydroxy 3 amyl phenyl) pentanoic acid, 4-( 44hydroxyphenyl) '-4- Z-hydtoxwel-chlorophenyl) brorno phenyl)-pentanoic': acid; 4 (4hydroxyp henyl)=4= (2-hydroxy-4-nitro phenyl) '-p entanoic acid; 4- (4-hydroxydimethyl phenyl pentarioic acid, 5;5*- bis(-4'- hydroxy phenyl) hexanoic acid, 5,5-bis (4-hydroxyl-3-nitro phenyl) hexanoic acid, and 5,5-bis(4*hydroxyl-3-chloro phenyl) hexanoic. acid; a 3

In 'Exaniplesl to. '.17.=inclusive,- thealdehydecan be: re. placed by; other aldehydesv including acetaldehyde; propionaldehyde, n-butyraldehyde," isobutyraldehyde, valeraldehyde, capronaldehyde, heptaldehyde .aswell as the more: complex aldehydes such as fu'rfural.

In Examples 10. to 12 .inclusive, the phenol modifiercan betreplaced thy. other; phenols :including 1 ortho, meta, and para cresol, 2,4 xylenol, 3,4 xylenol, 2,5 xylenol, 3,5 xylenol, p-phenyl phenol; p cyclohexylphenol, and p-tertamylphenol. p

In Examples 1 1 3 "to 17 inclusive, the ammonia-derivative can be replaced'by-other materials which havea NH' group with the free valences being-filled byhydrogenor carbon atoms. This'therefore includes" amides and -primary and secondary amines such' asthe -ureas, thioureas;

melamines;sulfonamides; and'alkyl substituted derivatives thereof.- It is only necessary thatthe material becapable of condensing-with an aldehyde.

OPERABLE EROXIDES- Illustrative of theepoxidecompositions which-may* be employed in this invention are the complex epoxide resins which are polyether derivatives of polyhydric phenols with such .polyfunctional couplingagents as polyhalohydrins, p olyepoxides, or epihalohydrins.

compositions may be describedas polymeric polyhydric, alcohols, having alternating aliphatic. chains and nuclei. connectedto each other. by ether linkages, containing, terminal epoxide groups andjfr'eefrom functional groups: other than epoxideand hydroxyl groups. It should be. understood that: significant amounts of. the monomeric reaction products are often present. This would be illu sw tratedIby IIIto V below where n equals zero, Prepar'a-l tion of these epoxide materials as welli'as. illustrative examplesare described in U.S.'.'.pat,ents,,2;45,6;408, 2,503}, 726, 2,615,007, 2,615,008, 2,668,807; 2,688,805; and

2,698,315. ,Well known commercial examplesof these resins are the Epon resins marketed by the Shell Chemical Corporation. Illustrative of the preparation of these epoxide resins are the following reactions wherein the difunctional coupling agent is used in varying molar excessive amounts:

Polyhydri c phenol and an epihalohydrin bis(hydroxyphenyl)isopropyli'dene excess epichlorohydrin I QEHCHLO alkali Polyhydrlc phenol and a polyepoxlde bls(hydroxypheny1)isopropylldeneI+Texcess butylene dioidde O 1 C HkHCHOHGIEh- O' ([JCHzCHOHCHOHCHLO heat 0 out on,

.O O CH UHEH OCHzCHOHOHLO' on, on, n; on, on, .III

Polyhydric phenol and a polyhalohydr ln b is(hydroxyphenyl)isopropylidene excess a-glycerol dichlorohydriu 0 C HkHOHrLO aqueous alkali As used in the above formulas, n indicates the degree of polymerization depending on the molar ratio of reactants. As can be seen from these formulas, the complex epoxide resins used in this invention contain terminal epoxide groups and alcoholic hydroxyl groups attachedto the aliphatic portions of the resin, the latter being formed by the splitting of epoxide groups in the reaction of the same with phenolic hydroxyl groups. -Ultimately, the reaction with the phenolic hydroxyl groups of the polyhydric phenols is generally accomplished by means of epoxide groups formed from halohydrins by the loss of hydrogen and halogen as shown by the following equation: a

Other epoxide compositions which may be used include the polyepoxide polyesters 'which may be prepared by esterifying tetrahydrophthalic anhydride with a glycol and epoxidizing the product of the esterification reaction. In the preparation of the polyesters, tetrahydrophthalic acid may also be used as well as the simple esters of tetrahydrophthalic acid such as dimethyl and diethyl esters. There is a tendency with tertiary glycols for dehydration to occur under the conditions used for esterification so that generally the'primary andsecondary glycols are the most satisfactory in the polyester formation. Glycols which may be used in the preparation of this polyester composition comprise, in general, those glycols having 2 hydroxyl groups attached to-separate carbon atoms and free from functional groups which would interfere with the esterification or epoxidation reactions. These glycols include such glycols as. ethylene glycol, diethylene glycol, triethylene glycol," tetlramethylo o on, on, n an. on, v tion and regulating the epoxidation reaction, polyepoxides having up to 12 or more epoxide groups per molecule may be readily prepared. These polyepoxide polyester compositions as Well as their preparation. are more fully described in a copending application having Serial No.

503,323, filed April 22, 1955.

Polyepoxide compositions useful inthis invention also include the epoxidized unsaturated natural oil acid esters, including the unsaturated vegetable, animal,- and fish oil acid esters made by reacting these materials with various oxidizing agents. These unsaturated oil acid esters are longchain aliphatic acid esters containing from about 15 to 22 carbon atoms. These acids may be esterified by simple monohydric alcohols such as methyl,

ethyl, or decyl alcohol, by polyhydric alcohols such as glycerol, pentaerythritol, polyallyl alcohol, or resinous polyhydric alcohols. Also suitable are the mixed esters erol and pentaerythritol, These, epoxidized oil acid esters may contain more than 1 up to 20 epoxide groups per molecule. The methodof epoxidizing these unsaturated oil acid esters consists of treating them with various 7 oxidizing agents, such as the organic peroxides and the peroxy acids, or with one of the various forms of hydrogen peroxide. A typical procedure practiced in the art consists of using hydrogen peroxide in the presence of an organic acid, such as acetic acid and a catalytic material, such as sulfuric acid. More recently epoxidation methods have consisted of replacing the mineral acid catalyst with a sulfonated cation exchange material, such as the sulfonated copolymer of styrene divinylbenz'ene.

The epoxidecompositions which inay-be usedfin'prethrough its unsaturatedportion; In the polymerization Of'the'se ethersthere is probably some polymerization occurring through the epoxide groups, and in addition some splitting of the epoxide groups toformrhydroxyl groups so that pure compounds are not usually obtained.

Other aliphatic polyepoxides useful in thisinvention may be illustrated by the poly(epoxyalkyl) ethers derived from polyhydric alcohols. These materials may, in gen-. eral, be prepared by reacting an aliphatic polyhydric alcohol with an epihalohydrin in the presence of a suitable catalyst and in turn dehydrohalogenating the product: to produce the epoxide composition. The production of these epoxides may be illustrated by the reactionofglycerol with epichlorohydrinin the presence ofboron' trifluoride followed by dehydrohalogenatiomwith sodium alumi-nate as follows:

CHQOH 011011 anouonroi CHQOH O OHzOCHzOHOHCHzCI CH2OCH2CHCH| 0 Naaio, CHOOHzGHOHCI-I CI 01100131011031,

0 CHgOCHzCHOHOHnCI CHBOCHQGHOH] VII -It is to be understood that such reactions do :not give pure compounds and/that the halohydrins formed andthe. epoxides derived therefrom are of somewhat varied char acter depending upon the particular reactants, their pro-;

portions, reaction time anddemperature. 'Zln additionzto epoxide groups, the epoxide compositions may be characterized by the presencerof hydroxyl groups and halogens. grou'ps-and halogens whieh are attached to adj acent-carbon-atoms. Some halogensmay'not be removed in-thisstep in the event that the proximate carbinol 5 group has been destroyed by reaction with an epoxidegroup These halogens are relatively unreactivefand are not {to be consideredas functional groups in the conversion of thereaction "rn-ixture of -this invention. 7 T l'l 6p1"pal'flt-lOH&Of a largenumber=of these mixed polyepoxides is describedilk-the Zeeh patents,- us; 2,538,072, 2,581,464, and-= 2,712,0O0J- Still other polyepoxides which} have been found to be-valr 1able are such epoxide compositions as 'di= epoxy butane-, di'glycid ether, and epoxidizedpoly-- butad-iene. 7

immediately following will .beadescription or illustration-of preparations of polyepoxideswhich'. will be used iii-examples of compositions of this invention.-

The complex: resinous polyepoxides used in the examples' and illustrativeof the commercially prepared products ofthis=type are theE'pon resins marketedby- Shell- Chemical Corporation. Thefollowing table gives the tproperties' of some Epon resins which are prepared by-th'e-condensationinthepresenceof alkali of-bis(4- hydroxyphenylyisopropylidenewitha molar exeess of epichlorohydr ininvarying amounts. 7

1 B ased on 40% nonvolatile in butyl Garbitol at 25 C.

Dehydrohalogenation affects only those hydroxyl Examp PREPARATION-OF POLYESTER FROM TETRAHYDROR PHTHALIC ANHYDRIDE AND ETHYLENEGLYCOL In a 3-necked flask provided with a thermometer, mechanical agitator, and a reflux condenser attached through a water'trap was 'placed'a mixture of '3 mole oftetrahydrophthalic anhydride and 2 mole of n-butanol'. After meItingLthe tetrahydrophthalic anhydride in the presence of the butanol, 2 mols of ethylene glycol were added. The reaction mixture was gradually heated with agita tion to 225 C. at which point a suflicient amount of xylene Was-added to give refluxing at esterification temperature. The reaction mixture was then heated with continuous agitation at 225-235 C. until an acid value of 4.2 was obtained. This product gave an iodine value of 128.

EPOXIDATION-OF- THE POLYESTER RESIN In a 3- necked flask provided with a thermometer, a mechanical'agitator, anda-reflux condenser was placed 107 partszof the dehydrated acid form of a cation exchange resin (Dowex 50X-8, 50100- mesh, Dow Chemical Company, a:sulfonated styrenedivinylbenzene copolymer containing, about 8% divinylbenzene, the percent divinylbenzene serving-to control the amount of crosslinkage. The Dowex resins are discussed in publications entitled Ion Exchange Resins No. l and Ion Exchange Resins No. 2, copyright 1954 by Dow Chemical Company, the publications having form number Sp32254, and Sp 31 -354, respectively), and 30 parts glacial acetic acid. The mixture of cation exchange resin and acetic acid was allowed to stand until the resin had completely taken up the acid. To this mixture was added 200 parts of the polyester resin dissolved in an equal weight of xylene. To the continuously agitated reaction mixture was added dropwise over a period of 45 minutes to 1 hour, parts of 50% hydrogen peroxide. The reaction temperature was held at 60 C. requiring the application of some external heat. (-In .some preparations involving other polyester--,resins, suffi'cient exothermic heat is produced during than 1"milliliter of 0.l N sodium thiosulfate in aniodometrjic determination of hydrogen peroxide.

resin filter cake; The acid "value ofthe total resin solution,was 42; The percentnon-volatile of this solution amounting to 400'fparts was 50. This 400 parts'of'solu- 'tion was thoroughly mixed with 110"parts ofthe' dehydrated basic form of Dowex 1 (an anion exchange resin of the quaternary ammonium type. Dowex 1 is a styrenedivinylbenzene copolymer illustrated by the formula RRQNtGHr where R' represents :the styrene-divinylbenzenematrix: andfR iszamethylz group, manufactured by. v the- -Dow. Chemical..Company).' The resulting mixture wastthen;filtered.ifollowed by pressing as much of ;the.

solutionras possible from-the'anion.exchange resin cake.

Thisproductzhad an acidfvalue: of 4:5' and'an -epoxide. equivalent :of 288izbasedon anon-volatile resin content ofi42..0.%.-. Theepoxidervalues asdiscussed herein .were

determinedzbywrefluxing 'for 30' minuteseaQ-gram sample.

with 50umilliliterseof pyridine hydrochloride .in excess pyr1din'e.-..,.(The;pyridine hydrochloride solution was presodium hydroxide; v

i V Example19' i Following. the-proc edurekof Example. 18-, .a polyester.

resin was prepared from 5'r nols of tetrahydrophthalicam hydride, 4 mols of diethylene glycol, and 2 mols of n les 18" through 20 describe the preparation or a The. product was then'filter'ed, finally pressing the cationexchange butanol. Thisproduct had an acid value of 5.3, and an iodine value of 107. This polyester resin was epoxidized in the manner previously described to give an epoxide equivalent weight of 371 on the nonvolatile content. The nonvolatile content of this resin solution as prepared was 40.2%. g

Example 20 The process of Example 18 was followed to obtain a.

polyester resin from 1.1 mols of tetrahydrophthalic anhydride, 1 mol of 1,4-butanediol and 0.2 mol of n-butanol.

The product had an acid value of 8.6. This polyester resin was epoxidized in the same manner to give an epoxide equivalent weight of 292 and an acid value of 5.2 on the nonvolatile content. The nonvolatile content of this resin solutionwas 41.9%.

Examples 21 and 22 describe the preparation of epoxidized vegetable oil acid esters.

, Example 21 EPOXIDIZED SOYBEAN OIL ACID MODIFIED ALKYD RESIN a. Preparation of with a condenser was added 290 parts of white refined soyabean oil. While bubbling a continuous stream of nitrogen through this oil the temperature was raised to 250 C., at which temperature 0.23 part of litharge were added and the temperature held at 25 C. for '5 minutes. While holding the temperature above 218 C., 68 parts of technical pentaerythritol were added after which the temperature was raised to 238 C. and held until a mixture of 1 part of the product and 2% parts of methyl alcohol showed no insolubility (about 15 minutes). At this point 136 parts of phthalic anhydride were added and the temperature gradually raised to 250 C. and held at this temperature for 30 minutes. At this point the condenser was removed from the kettle and the pressure reduced somewhat by attaching to a Water aspirator evacuating system. With continuousagitation the mixture was held at 250 C. until the acid value had reached 10.5. At this point the resin was thinned with xylene to 48% nonvolatile content having a viscosity of H (Gardner bubble viscosimeter),

b. Epoxidation of a soyabean oil acid modified alkyl resirz.In a 3-necked flask provided with a thermometer, a mechanical agitator and a reflux condenser was placed 70 parts of dehydrated acid form of a cation exchange resin (Dowex 0X-8) and 15 parts glacial acetic acid.

The mixture of cation exchange resin and acetic. acid was allowed to stand until the resin had completely taken up the acid. To this mixture was added 315 parts of the alkyd resin solution described in the above paragraph and 190 parts of xylene. To the continuously agitated reaction mixture Was added dropwise 38 parts of 50% hydrogen peroxide. The reaction temperature was held at 60 C. until a milliliter sample of the reaction mixture analyzed less than one milliliter of 0.1 N sodium thiosulfate in an iodometric determination of alkyl resin.-To a kettle provided.

lExamples 23 and .24 describe the preparation of aliphatic polyepoxides. r Y

I d I Example 23 Ina reaction vessel provided with a'mechanical stirrer and external cooling means was placed 276 parts of glycerol and 828 parts of epichlorohydrin. To this reaction mixture was added 1 part of 45% boron trifluoride ether solution diluted with 9 parts of ether. The reaction mixture was agitated continuously. The temperature rose to 50 C. over aperiod of 1 hour and 45 minutes at which time external cooling with ice water was applied The temperature was held between 50 and 75 C. for 1 hour and minutes. To 370 parts of this product in a reactionvessel provided with a mechanical agitator and a reflux condenser was added 900 parts of dioxane and 300 parts of powdered sodium aluminate. With continuous agitation this reaction mixture was gradually heated to 92 C. over a period of 1v hour and 50 minutes, and held at this temperature for '8- hours and 50 minutes. perature, the inorganic material was removed by filtration. The dioxane and low boiling products were removed by heating the filtrate to 205 C. at 20 mm. pressure to give. a pale yellow product. The epoxide equivalent of this product was determined by treating hydrogen peroxide. The product was then filtered,

The resulting Adrnex, 710, anepoxidized soyabean, oil having an equivalent Weight to an epoxide of 263, was dissolved .70 in methylethyl ketone to a non-volatile content of 50%.

Adm ex 7 10, a product of the Archer-Daniels-MidlandfY: Company, has an, acid .value of 1, a viscosity of 3.3

stokes at 25 C. an d an average molecular weight of a l-gram sample with an excess of pyridine containing pyridine hydrochloride (made by adding 20 cc. of concentrated hydrochloric acid per liter of pyridine) at the boiling point for 20 minutes and back-titrating the excess pyridine hydrochloride with 0.1 N sodium hydroxide using phenolphthalein as indicator and considering one HCl as equivalent to one epoxide group. The epoxide equivalent on this product was found tobe 152.

Example 24 minutes during this 8-hour period. After the reaction mixture had stood overnight, the volatile ingredients were removed by vacuum distillation. The distillation was started at 19 mm. pressure and a pot temperature of 26 C. and volatile material finally removed at a pressure of 3 mm. and a pot temperature of 50 C. The residual product had a molecular weight of 418, and equivalent weight to epoxide content of 198, the yield amounting to 250 parts.

GENERAL REACTION CONDITIONS AND CHAR- ACTERISTICS OF THE NEW COMPOSITIONS In making the new. compositions, the polyepoxides and aldehyde condensates are admixed in suitable proportions and reaction will proceed merely by the application of heat. More specifically the reaction is eifected by heating the mixtures at elevated temperatures, usually in the range ofabout 250 C. Catalysts are unnecessary, but in certain cases it may be desirable to speed up the reaction by theuse of catalysts, such as boron trifluoride adducts, sodium phenoxides, and mineral acid type catalysts.

The reaction mixtures and final reaction products of this invention can be prepared by using varying ratios of epoxide to aldehyde condensate. The quantities of reactants employed in a given instance will depend upon the characteristics desired in the final product. Flexible conversion products can, be obtained from a hard epoxide by employing relatively large amounts of a low-melting 75 aldehyde condensatesofflexibility' may be imparted by After cooling the room tem 15 larger-amounts ofa soft epoxide. In' general, operable products are those in which the ratio of-epoxide to a1dehyde condensate ranges' from about 6:1 to 1:6 with the preferred range, because of the general overall characdroxyl? or carboxyl groups, and reaction" of epoxide groups with active-hydrogen attached to a nitrogen" atom,

all of'whieh talc-"e place to "some extent 'sirnultaneouslyjin forming the final products- 1 Thesp-resent invention provides a wide range of reaction teristi'cs, b'eing from'2: l 'to 1:2.

Compositions containingthe polyepoxides and the aldecompositions and products including initial mixtures of hyde condensates may be used as mixtures or: at varythe polyepoxides, and the aldehyde condensates, partial or irig; intermediate stages of reaction. The initial mix-. intermediatereaction products ofzsuchmixturesand comtures or intermediate reaction products which" aresolupositionsucontainingxsuch:intermedi'ate:reaction products ble in common organic solvents may beublended in solu- 10 asuwellrassfinahreactionrproducts... In general, the initial tion inproper. proportions and the solutions. then applied mixtures; as well .as. the intermediate :reaction products. as .an impregnantfor'fabrics or paper, or. forthe formaunless -too highly. polymerized;.arewsolublezinsolvents of tion of protective coating films. Subsequent h'eatingfuncthe lacquer. type, .su'chvasketone or:- estersolvents.- tions to remove. the solvent 'andbririg about polymeriza- I ln1additionito having outstanding physical:.properties,fl tion. to the insoluble, infusible' state. For other uses, uch as hardness, toughness,andflexibility, the finalii -i' the initialf'or intermediate mixture may be used without ffisi 1 ,:.iusolub1e products. have outs anding. chemical a solvent, giving .directly a composition. which, on the properties, such as highnresistancer to;oxidation, waten. application of heat; converts t an infusible, insoluble alkali, acids and organicsolvents. It has also been obfinal product. 7 served that the final conversion products possess unusually For thepreparation of 'semi-liquidadhesive composi- "g adhesion to mostsllrfacesilichlding mfital; glass, tions,..low-1nelting; or syrupy polyepoxides would be used wood, and plastics. This .property of outstanding adwith a low-melting aldehyde condensate. For various: h ionto wi v ri y of'surfaces gi the je P other applications,. higher melting compositions are de ucts high potential value for use in formulating adhesives. sirable in which case partially polymerized mixtures of I This. property is alsoof extreme valuein formulating protliepolyepoxide andaldehyde condensate could advan- 25 tectivecoating fil'rns for-use on many types of'surfaces. tageously be usedi An alternative method of obtaining Theadhesion charactefls'ticsIare probably dueto the fact the higher melting compositions is to choose higher inelt-' that n ill-the 0I1VeIted;.iIlfu$ib1 State, thep in'g forms of the polyepoxide and aldehyde condensate. tidns contain anrelatively higli pe centage of'highly polar In making the' new. compositions andproducts herein. g p such 5 groupsrestef g p and'aloholic described, the polyepoxides andthe aldehyde condensates and phenolic hydroxyl groups. Despite the high" per may be used in regulated proportionswithout the addition. n gc f p gr ps in the l l inf i l pro ofother materials. For certainuses, other'cornponents' ucts ofthis invention th'etolerancefor water is usuallyv are. often advantageously. added, including filling and" PR y t6 the high molecular weight and compounding materials, plasticizers, pigments, etc. Com: rigiflcrOS'S-linked structure of "the final compositions. iti hi h d t iv e hat brittle products Examples 25 r0173; inclusive, illustrate the preparation on conversion to theinsoluble, .infusible stateare advanof i soluble, fiisiblc protective coating films from the tageously eompoundedwithplasticizers.. For mo t. ap compositions ofthis invention. In the preparation of pli'cations,-. it .ispossible to obtain suitable flexibility and the composition for heat curing to form'the protective toughness by regulatingrthe proportions andtypesof. recoating films, each of "the aldehyde condensates and the acting.ingredients,.,thereby obviating. the need for plasti- 40" polyepoxide's with the exception of 'epoxidized'polyesters cizers. were dissolved in methyl ethylketone to. a nonvolatile.

The application of heat to themixtureshereinset forth content of 4060-%. The'epoxidized polyesters were-.used may. involve several chemical. reactions. It will be apatth n n i aHdYiII the n 'w i i they w r preciat'ed that the reactions involved are'very complex prepared. some of th aldehyde cond nsates required a and the extent to which each .takes place will vary with mixtureof methyl 'ethyl ketone andbutanol to effect comthetemperature used in heat treating, the. period of time. plete solubilit'y Mixtures of the polyepoxides and'aldetherefor, and. with the particular types of polyepoxide ,v hyd'e condensates were found to be stable for extended 1 and aldehyde condensates, chosen. Whileit is not desired periods of time at normal temperatures. Mixtures of the tobelir'nit'ed by any theoretical explanation. of the exact S lllti n W spr on Panels with a .002" Bird applicanature of 'these reactions, it seems probable. that eo *torand'fthefilr'ns were. baked for periods of '30to version to the final polymericfproducts is accompanied. minutes attemperatures ranging from 2'00 C; Proby direct polymerization of theepoxide groups inter 'se; portions as used. in the following. table refer to parts by reaction of the epoxide groups with. methylol hydroxyl weight and areibased'on-the nonvolatile content of the groups; reaction of the epoxide groups with phenolic hysolutions of reactants.

Catalyst Conversion Filmresistance Example Alde- N0. Polyepoxide Parts hydecon- Parts v Hours 5% densate Type Parts 'Time" Temp. 11,0 at aqueous '(hrs.) '('O.)' (1003C) NaOHEtat" Epon 864.- 5 6. 1 Epon I001 5 3.5 Epon 1004 5 1. 9 Epon 1007 5 1. 2 -do 5 1.2. do 5 2:0

Epon 10o1 5 3 7 hr. 30 min... 1 hr. 15 mint do 5- i3 30min 9hr. Epon1004." 1 5 200 451:11il1- 9hr,

'5 1 175 1 hr. 45 s hr. 30mm.

do 1 5 200 inn-45mm..- 9111 ."45 min.

do I s 17s 15 min; 3hr. 15min. do-.' "5 ifgr 175' 1hr.45 10mins mints Oa5a1yst Conversion Film resistance Exam 1e Alde- N 0. Polyepox'idei Patts hyde 0011- Parts 1 Hours 5% densate Type 1 Parts Tune Temp. H at aqueous (hm) 0.) (100 0.) N35??? gat 11110111007- 0. 5 175 15 1111.11 1 hr. 15 min.

%x. 6 ....d5 5 :2 0.5 175 15111111 1111.15111111. d 5 0.5 175 mi11 4h1.451n111. 1 1 5 i :2 0.5 175 15111111 5111.15111111. do 5 h 0.5 175 15111111 5111. 45111111.

. *x.1 2.0 do 5 10m 11 0.5 175 4511111 5111.15111111. 11 1511354-.-. 5 f 0.5 175 3111-.45111111- 5111-.15111111. 13 10111001.-- 5 h: 0.5 175 3111.15111111 45111111. 45 .115 5 f :3 0.5 175 15111111 3111. 45111111. .47 1g04 5 0.5 175 3hr.15n1i11 1hr.15mi11. 4s 11 111111007..- 5 i5: 0.5 175 15min 10111. 45111111.

0 5 175 7111. 45 111111. f? 175 4111. 45111111 2111.45 min. f; 175 1111. 45111111.. 2111. 45111111. 215 175 3111. 45111111 30111111. 2.1 175 1 hr. 15 min min. 2.3 175 1hr.15min 30 min. 2.7 175 1hr.15min 30 min. 4.3 175 111111 30111111. 2.0 175 1h1.15 111111- 111115111111 7.8 175 4hr.45 min 11 13.5 175 3111245 min-.. 10 mm .9 6.4 175 4111.45 min 15111111 5 13.7 175 9hr. 30 min 30 mm .5 5.0 175 1111301111... 2111 5 5.7 175 1111. 30111111- 15111111 5 175 1h1.50 111111-.. 1111. 5 I4 1215 175 1111. 30111111"- 30111111 5 .4 5.3 175 1111. 30111111--. 2111 5. 14.6 175 6111.30111111--. 30 min. 5 .5 7.3 175 1111 30 min-.. 15 mm 5 175 1111 30111111. 30111111 5 I1 11.2 175 5111. 3011111--- 30111111. 5 175 2111.30 111111.-- 10111111. 5 I1 515 175 1111. 30111111... 45111111. 5 23.5 175 9h1'.3Omin 30 min. 5 g? 175 2111. 30111111. 10111111. 5 I 1115 175 5111 1111.15111111. 1 4.4 175 11111.30111111 10111111. 1 2.2 175 3111. 30111111... 15111111. Ep011864 5 175 1hr. 30 min..- 30hr. I Ex. 4..-. 5.5 -85 d0 5 g i 1.1 150 30m111 6hr. x. 10.5 v 55 do 5 4'5 150 3111.50111111 1111. 30111111. 87 Epo111001 5 gig 150 lhl 10 hr.

Ex. 9 3.5 .110 5 as 150 1hr 58hr. 89 Epon1004 5 {553 5: 51 150 15 min 1 28hr.

Ex. 0 1.0 00 .115 5 07 150 1111 511 111. 01 Epon1007 5 150 2111. 30111111... 15111.

Ex. 1 2.0 92 --do- 5 M 150 1111 10 hrs. 30 111111. 03 15115111001... 5 f 175 1111 71m 94 1311011864...- 5 150 1hr 1hr.30m1n. 05 11115111001"- 5 i 150 5111 1111. 115 E o111004..- 5 fi Ex. 5.: 1.2 4 93 5 0.6 45111111 27111. 30111111. 9 Epon1004 5 i 150 45111111 1111. 100 11115111007--- 5 git: 150 1111. 30111111.-. 1111.

1 Catalyst Conversion resistance Example Alde- N o. Polyepoxide Parts hyde eon- Parts Hours 5% densate Type Parts Time Temp. H5O at aqueous (hrs) 0.) (100 0.) NaOH (at 152 Ex. 23 5 175 11 hr. 45 111111-- 1 hr. 15 mm. 153 Ex. 23 5 175 3 hr 3 hr. 154 Ex 23 5 :2 175 1 hr 1 hr. 15 min. 155 Ex. 23 5 1 2:8 175 2 hr 30 min.

Ex. 24 1 I 2 hr. 15 min. Ex. 24 1 3hr.15 Ex. 24 1 :8 20 min. Epon 1001..- 1. 5 1. 5 2 hr. Epon 562.... 2.0 1.0 20 min Epon 1001-.. 1. 5 1. 50+ hr Epon 1004... O. 1.0 1 hr. Epon 1001.- 1. 5 1. 0 50+ hr. Epon 1004... 0.5 1.0 2 hr. 30 min Epon 1001..- 1.0 0. 5 50+ hr. Epon 562.-.. 1. 0 1.0 2 hr. Epon 1004... 2. 0 I 20 hr. 158 Epon 1001..- 0. 5 g min 159 Epon 552.--. 0. 5 5 min 170 Epon 1001.-. 0. 75 24 hr. 171 Epon 502---. 0. 5 Z min 172 Epon 552.-.. 0. 5 f f8 10 min 173 Epon 1004... 0. 5 i 200 4 hr. min... 10 min It will be appreciated that the flexibility of the conversion products of this invention may be controlled by proportioning the reactants used, and by the addition of varying amounts of plasticizers. Typical lacquer type plasticizers having polar characteristics such as the sulfonamide plasticizers and certain polyester plasticizers are suitable for admixture with the reaction mixtures to obtain the desired flexibility.

Examples 174 through 186 illustrate the preparation of hard conversion products which may be used for the preparation of flexible coating films upon the addition of suitable plasticizers. The reactants were used as nonvolatile methyl ethyl ketone solutions, and the parts referred to in the examples are parts by weight based on nonvolatile content.

Example 174 A reaction mixture was prepared by admixing 10 parts of Epon resin 864, 80 parts of the condensate of Example 9, and 10 parts of condensate of Example 15. The mixture was spread in wet films of .002" thickness and the films were then cured by baking them at 175 C. for a period of 30 minutes to form converted products which were insoluble and infusible.

Example 175 A reaction mixture was prepared by admixing 10 parts of Epon resin 864, 10 parts of the condensate of Example 3, and 80 parts of the condensate of Example 14. The mixture was spread inwet films of .002" thickness and the films were then cured by baking them at 175 C. for a period of 30 minutes to form converted products which were insoluble and infusible.

Example 176 A reaction mixture was prepared by admixing 25 parts of Epon resin 864, 25 parts of the condensate of Example 3, and 50 parts of the condensate of Example 15. The mixture was spread in wet films of .002" thickness and the films were then cured by baking them at 175 C. for a period of 30 minutes to form converted products which were insoluble and infusible.

Example 177 A reaction mixture was prepared by admixing parts of the polyepoxide polyester of Example 19, 5 parts of the condensate of Example 2, and 15 parts of the condensate of Example 13. The mixture was spread in wet films of .002" thickness and the films were then cured by baking them for 30 minutes at a temperature of C. to form converted products which were insoluble and infusible.

Example 178 A reaction mixture was prepared by admixing 5 parts of the polyepoxide polyester of Example 18, 15 parts of the condensate of Example 5 and 80 parts of the condensate of Example 14. The mixture was spread in wet films of .002 thickness and the films were then cured by baking them for 30 minutes at a temperature of 175 C. to form converted products which were insoluble and infusible.

Example 180 A reaction mixture was prepared by admixing 25 parts of the polyepoxide polyester of Example 18, 25 parts of the condensate of Example 4 and 50 parts of the condensate of Example 15. The mixture was spread in wet films of .002" thickness and' the films were then cured by baking them for 30 minutes at a temperature of 175 C. to form converted products which were insoluble and infusible.

Example 181 A reaction mixture was prepared by admixing 10 parts of the epoxide of Example 21, parts of the phenolaldehyde condensate ofyExample 5,, and 85 parts of the ammonia derivative-aldehyde condensate of Example 15 The mixture was spread in wet films of .002" thickness and the films were then/cured by baking them at 175 C. for a period of 30 minutes to form converted products which were insoluble and infiusible.

. Example 182 A reaction mixture was prepared byadmixing 25 parts of the epoxide of Example 22, 25 parts. of the phenolaldehyde condensate of Example 2, and 50 parts of the ammoniaderivative-aldehyde condensate of Example 14.

The mixture was spread in wetfilms of .002 thickness and the films were then cured by baking them at 175 C.

for a period of 30 minutes to form converted products which were insoluble and infusible.

Example 183 A reaction mixture was prepared by admixing 80 parts of the polyepoxide of Example'24, parts of the condensate of Example 9, and 1 0 parts of the condensate of Example 14. The mixture was spread in wet films of .002 thickness and the films were then cured by baking them at 175 C. for a period of3'0 minutes to form converted products which were insoluble and infusible.

Example 184 A reaction mixture was prepared by admixing parts of the polyepoxide of Example 24, 80- parts of the condensate of Example 9, and. 5 parts of the condensate, of

Example 14. The mixture was spread in wet films of .002" thickness and'the films were then curved by baking the mat 175 C. for a period of 30 minutes to form converted products which were insoluble and infusible.

Example 185' A reactionmixture wasiprepare'd by admixing 25 parts of thejpolyepoxideof Example 24, 25. parts of the condjensate of' Example 5, ,and 50 parts of the condensate of Example, 1 5. They mixture was spread in, wet films of .00 2""thickn'es's, and the. films. were then cured by baking. them at 175 Cl for a period of 30 minutes to form converted products which were insoluble and infusible.

Example 186 A reaction mixture. was prepared by admixing 10 parts of the polyepoxide of Example 23., 1.0 parts of. the con densate of Example 3, and, 80 parts of the condensate of Example 151 The, mixture was, spread in wet films of .002" thickness and the films were. then cured by. baking them at, 175 C. for a period'ofi 30 minutes to form con: verted products which were insoluble and infusible.

It should be appreciated that the invention is not to be construed to be Iimited by the-illustration examples. It is possible to: produce; still. other. embodiments without departing fromthe inventive concept, herein disclosed. This applicationis a.,continuation-in-part of the Greenlee copending applications S.N. 534,407, and 550,766, filed September 14, 1955, andDecember. 2, I955, respectively, now, abandoned.

It is claimed and desired to secure by Letters Patent:

1. A composition of matter comprising the condensation product obtained by heating A) an organic polyepoxide having an average of more than one epoxide group. per molecule wherein the epoxy oxygen atom is linked, to adjacent: carbon. atoms and (B) a polycarboxylic acidwhichds a fusible-condensate. of. (a); a low molecular weight. mono-aldehyde and b) av 4,4bis( hydroxyaryl) pentanoic acid wherein the hydroxyaryl radi? cal is; a-memberofthegroup-consisting of unsubstituted.

hydroxyphenyl gand ringsubstituted -hydroxyphenyl wherein the hydroxy group of said member is in a position.

consisting of chloro, bromo,. nitro and al-k-yl groups offrom- 1-5 carbon atoms, with said hydroxyphenyl radical having hydrogen on at least one position other than one meta, in relation to the hydroxy group wherein. the ratio of (a) to (b) is from 015-4 moles of (a) per mole of (b); and wherein the reactive functional groups of (A) and- (B) are present in anequivalent ratio-of from 6:1. to 1:6.. 2. The composition of claim 1 wherein the pentanoic acid. is 4,4-bis(4-hydroxyphenyl)pentanoic acid.

3. The composition of claim 1 wherein the pentanoic acid. is a. 4,4-bis(4-hy droxy, alkylphenyDpentanoic acid.-

4'. The composition of claim 1 wherein said polyepoxide (A) is acomplex epoxide which is'a polymeric polyhydric alcohol having alternating aliphatic chains and aromatic nuclei united through ether oxygen and terminating in epoxy-substituted. aliphatic chains.

5. The composition of matter of claim 1 wherein said polyepoxide (A), is an epo'xidi zed polyester of tetrahydrophthalic acid and a glycol, wherein the epoxy oxygen atoms are each linked to adjacent carbon atoms in the nucleus of said acid.

6. The composition of matter of claim 1 wherein said polyepoxide. (A) is an 'epoxidized ester. of. an unsaturated natural fatty oil acid containing about 15-22 carbon atoms, and having its'reactive groups selected from the class consisting of epoxy and hydroxy.

7.. The. composition of: matter of claim 1 wherein said polyepoxide (A) is an. aliphatic polyepoxide selectedfrom the group; consisting of bis.(glycidyloxy)butene, triglycidyl glyceryl ether; diepoxy butane, and diglycide ether.

8. The composition of claim 1 wherein the reactive functional groups. of (A) and (B) are present in an equivalent ratio. of from about 2: 1 to 1:2.

9. A composition of matter comprising; the condensation product obtained by (heating; (A). an organic poly epoxide= having an average. of more than one epoxide. group per- .molecule wherein the epoxy oxygen atom. is. linked to adjacent carbon atoms, (B) a polycarboxylic acid which is a fusible condensate of (n) a low molecular weight mono-aldehyde: and (-b) a. 4,4.-bis-(hydroxyaryl-.)pentanoic acid wherein the hydroxyarylradical is.

a member of thehgroup consisting of unsubstituted hydroxyphenyl and ring substituted hydroxyphenyl wherein the hydroxy group of said member is in a position other. than one meta' to'the point of attachment of said member to the pentanoic acid, any substituent onthe hydroxyphenyl being a member selected from the group consisting of chloro, bromo, nitro and alkylgroups of from. l:5 carbon; atoms,. with said hydroxyphenyl. radical having l'lYdITOgfiILOID atyleast one positionother than one meta, in relation. to} the hydroxy group. wherein the ratio of: (a to (12.) i's;f'rom 0.5-4 moles of (a) per mole. of (17.), and .(C) a fusiblecondensate of a low molecu lar weight mono aldehyde with at least one organic am.-

monia derivative selected from the. group consisting-of urea, thio-urea, melamine, toluenesulfonamide and alkyl substituted derivatives thereof, wherein the reactive functional groups of (A) and (Bel-C) are present in an equivalent ratio:of from about 6:1 to 1:6 with (C) constitutingnomore than of B+C).

10. A compositionof' matter comprising. the condensation productobtained by heating (A an organic polyepoxide having anaverage of more thanone epoxide group per molecule wherein the epoxy oxygen atom is a member of the group consisting of unsubstituted hydroxyphenyl-and ring substituted hydroxyphenyl wherein the hydroxy group of' saidmember is in a position a other than one meta to the point of attachment of said member to the pentanoic acid, any substituent on the 2,907,729 25 26 hydroxyphenyl being a member selected from the group References Cited in the file of this patent consisting of chloro, bromo, nitro and alkyl groups of UNITED ATES PATENTS from 1-5 carbon atoms, with said hydroxyphenyl radical ST having hydrogen on at least one position other than one 1923 321 Meigsl 1933 meta, in relation to the hydroxy group wherein the ratio 5 2,521,911 Green 66 SePt' 1950 of (a) to (b) is from 0.5-4 moles of (a) per mole of 2528360 Gmenlee 1950 (b), and (C) a fusible condensate of a low molecular 2,699 A13 Seagren et 1955 weight mono-aldehyde with a phenol, wherein the reactive functional groups of (A) and (B+C) are present OTHER REFERENCES in an equivalent ratio of from about 6:1 to 1:6 with 10 Badel: 6t 1 Chem 4465-5 (C) constituting no more than 80% of (B+C). PY 111 Sclentlfic y-) y and 10, equation designated as. IV appearing as:

- column 13, lines 22 and 43, for "alkyl", in each occurrence, read UNITED STATESPATENT OFFICE, CERTIFICATE'OF' CORRECTION Patent No. 2,907,729 I October 6, 1959 Sylvan Owen Greenleet It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

I Column 2, lines 5', ll, 41, and column 3, lines 41 and 42', for "diphenolic acid, each occurrence, read Diphenolic Acid columns '9 2 should read 3 alkyd w; column 14, line 21, for "the room" read to room e;

column 16, line 32, for "usually" read me unusually column 23, line 01 33, for "curved" read cured line 34, for "the mat" read them at Signed and sealed this 17th day of May 1960.,

( EAL) Atteat:

KARL Hn .AXLDIE ROBERT 0., WATSON Attesting Officer Commissioner of Patents 

1. A COMPOSITION OF MATTER COMPRISING THE CONDENSATION PRODUCT OBTAINED BY HEATING (A) AN ORGANIC POLYEPOXIDE HAVING AN AVERAGE OF MORE THAN ONE EPOXIDE GROUP PER MOLECULE WHEREIN THE SPOXY OXYGEN ATOM IS LINKED TO ADJACENT CARBON ATOMS AND (B) A POLYCARBOXYLIC ACID WHICH IS A FUSIBLE CONDENSATE OF (A) A LOW MOLECULAR WEIGHT MONO-ALDEHYDE AND (B) A 4,4-BIS(HYDROXYARYL) PENTANOIC ACID WHEREIN THE HYDROXYARYL RADICAL IS A MEMBER OF THE GROUP CONSISTING OF UNSUBSTITUTED HYDROXYPHENYL AND RING SUBSTITUTED HYDROXYPHENYL WHEREIN THE HYDROXY GROUP OF SAID MEMBER IS IN A POSITION OTHER THAN ONE META TO THE POINT OF ATTACHMENT OF SAID MEMBER TO THE PENTANIOC ACID, AND SUBSTITUENTS ON THE HYDROXYPHENYL BEING A MEMBER SELECTED FROM THE GROUP SONSISTING OF CHLORO, BRONO, NITRO AND ALKYL GROUPS OF FROM 1-5 CARBON ATOMS, WITH SAID HYDROXYPHENYL RADICAL HAVING HYDROGEN ON AT LEAST ONEPOSITION OTHER THAN ONE META, IN RELATION TO THE HYDROXY GROUP WHEREIN THE RATIO OF (A) TO (B) IS FROM 0.5-4 MOLES OF (A) PER MOLE OF (B); AND WHEREIN THE REACTIVE FUNCTIONAL GROUPS OF (A) AND (B) ARE PRESENT IN AN EQUIVALENT RATIO OF FROM 6:1 TO 1:6. 